Polyethers and method for making the same

ABSTRACT

HYDROXY TERMINATED POLYETHERS ARE OBTAINED BY REACTING (1) EPOXIDE AND OXETANE MONOMERS WITH (2) A TELOGEN AT LEAST PARTIALLY SOLUBLE WITH THE MONOMERS, REACTIVE WITH SAID MONOMERS AND BEING SELECTED FROM THE GROUP CONSISTING OF ORGANIC HYDROXY CONTAINING COMPOUNDS, SULFHYDRYL CONTAINING COMPOUNDS, ALDEHYDES AND KETONES, SUCH AS METHANOL, HEXANEDIONE-2,5, ACETONE, ETHYLENE GLYCOL, TRIMETHYLOL PROPANE, ETC., USING (3) IN ADMIXTURE THEREWITH A CATALYSTS CERTAIN DOUBLE METAL CYANIDE COMPLEXES WHICH PREFERABLY HAD BEEN TREATED WITH ORGANIC MATERIALS LIKE ALCOHOLS, ETHERS, ESTERS AND SO FORTH. A FEATURE OF THE PROCESS OF THE PRESENT INVENTION IS THE PREPARATION OF HIGH MOLECULAR WEIGHT DIOLS, TRIOLS, ETC. WITHOUT APPRECIABLE END GROUP UNSATURATION, AND THE USE OF CERTAIN SOLVENTS WITH PARTICULAR MONOMERS AND CATALYSTS TO ALSO ACHIEVE THESE RESULTS. THE PRODUCTS OF THE PRESENT PROCESS ARE USEFUL AS NONIONIC SURFACE ACTIVE AGENTS, AS LUBRICANTS AND COOLANTS, AS TEXTILE SIZES, AS FILM FOR PACKAGING AND IN THE PREPARATION OF SOLID OR FLEXIBLE POLYURETHANES BY REACTION WITH POLYISOCYANATES.

3,829,505 Patented Aug. 13, 1974 3,829,505 POLYETHERS AND METHOD FORMAKING THE SAME Robert Johnston Herold, Akron, Ohio, assignor to TheGeneral Tire & Rubber Company No Drawing. Continuation of applicationSer. No. 13,773,

Feb. 24, 1970, which is a continuation-in-part of application Ser. No.479,333, Aug. 12, 1965, both now abandoned. This application July 7,1972, Ser. No. 269,631

Int. Cl. C07c 41/00 US. Cl. 260-611 B 6 Claims ABSTRACT OF THEDISCLOSURE Hydroxy terminated polyethers are obtained by reacting 1)epoxide and oxetane monomers with (2) a telogen at least partiallysoluble with the monomers, reactive with said monomers and beingselected from the group consisting of organic hydroxy containingcompounds, sulfhydryl containing compounds, aldehydes and ketones, suchas methanol, hexanedione-2,5, acetone, ethylene glycol, trimethylolpropane, etc., using (3) in admixture therewith as catalysts certaindouble metal cyanide complexes which preferably had been treated withorganic materials like alcohols, ethers, esters and so forth. A featureof the process of the present invention is the preparation of highmolecular weight diols, triols, etc. without appreciable and groupunsaturation, and the use of certain solvents with particular monomersand catalysts to also achieve these results.

The products of the present process are useful as nonionic surfaceactive agents, as lubricants and coolants, as textile sizes, as filmsfor packaging and in the preparation of solid or flexible polyurethanesby reaction with polyisocyanates.

This application is a continuation of prior copending application Ser.No. 13,773, filed Feb. 24, 1970 (now abandoned), which in turn is acontinuation-in-part of prior copending application Ser. No. 479,333,filed Aug. 12, 1965 (now abandoned).

The present invention relates to a method for making hydroxy terminatedpolyethers or polyether telomers and more particularly to a method ofmaking polyethers having more than one active hydroxyl group, and to theproducts of such methods.

It is an object of the present invention to provide a method for makinghydroxy terminated polyethers.

It is another object of this invention to provide' a method for makingrelatively low molecular weight liquid polyethers having a hydroxylfunctionality greater than one such as polyalkylene ether glycols,triols and so forth.

A further object is to provide hydroxy terminated polyethers which canbe liquid.

These and other objects and advantages of the present invention willbecome more apparent to those skilled in the art from the followingdetailed description and examples.

According to the present invention it has been discovered that hydroxyterminated polyethers can be obtained by reacting (1) epoxide andoxetane monomers with (2) a telogen at least partially soluble with themonomers, reactive with said monomers and being selected from the groupconsisting of organic hydroxy containing compounds, sulfhydrylcontaining compounds, aldehydes and ketones, using (3) in admixturetherewith as catalysts certain double metal cyanide complexes which havebeen treated with organic materials like alcohols, ethers, esters and soforth. Depending on the amount of telogen used the resulting polymersreferred to hereafter as telomers can vary from light oils to greasesand solids having at least a hydroxyl functionality of one. If di andhigher functionality telogens are used, the resulting telomers have ahydroxyl functionality approaching the functionality of the telogen.Additionally, it has been found that while certain catalysts containingacidic metal halide, e.g., Cl and Br, residues give narrower molecularweight distributions, they also give polymers with undesirableunsaturation (loss of OH functionality) particularly when certainepoxide monomers are used which are prone to isomerize to thecorresponding allylic alcohol but that this unsaturation may besuppressed by telomerization in certain basic solvents.

A feature of the process of the present invention is the preparation ofhigh molecular weight diols, triols, etc. without appreciable end groupunsaturation. For example, the catalyst presently used in makingpolyetherpolyols is KOH. However, the molecular weight of products madewith KOH appear to be limited to about 4000. While the diols producedwith KOH and by the method of this invention are of about the samefunctionality, i.e., hydroxyl groups per molecule, at 1000 molecularweight, at 2000 molecular weight and higher the diols produced with KOHhave significantly lower OH functionality than those produced by thepresent invention. Similar differences in functionality may be seen inthe case of triols at the 3000 and 4000 molecular weight levels. UsingKOH as a catalyst, the reaction of glycol and 1,2-epoxy butane does notprovide high molecular weight polymers.

TELOGEN AND TELOMER It is not precisely known what happens in thepresent process although it is believed that the telogen acts as a chaintransfer agent. The telogen is not believed to affect propagation butrather to institute chain transfer to produce polymers having rather alow average molecular weight and a narrow molecular weight distributionin certain instances. The alcohols, glycols, etc. react through theirhydroxyl group(s) and the mercaptans through their sulfhydryl group(s).It is believed that the basic reaction responsible for this effect istransfer of a proton from a hydroxyl group of an alcohol, for example,to a growing polymer chain with simultaneous transfer of the catalystfrom that growing chain to the oxygen of the hydroxyl:

(growing polymer chain) The ketones and aldehydes most probably firstenolize and then follow the above sequence. The efliciency of thisreaction is emphasized by the fact that as many as 500 telomer chainsper catalyst unit may be formed. The telogens should preferably beliquids as such or under the telomerization conditions of temperatureand pressure. However, solid telogens are useful. They, also, should besoluble in or at least partially soluble in the epoxide or oxetanemonomer. The extent of solubility should be at least a tenth of apercent by weight of the epoxide etc. The remaining material goes intosolution as it is reacted. These telogens should also be free of primaryand/or secondary aliphatic amino groups.

Telogens which can be used in the practice of the method of the presentinvention are organic hydroxy containing compounds such as primary,secondary and/or tertiary alcohols; diols and polyols; and other hydroxycontaining compounds such as the phenols. The corresponding organicsulfhydryl containing compounds, such as mercaptans or thiols,polythiols and the like can be used. Aldehydes and ketones includingdialdehydes and diketones can also be used; however, it is preferredthat the diketone should be one which does not form a conjugated doublebond in the enol form. The telogens, also, may contain 1,2-epoxide or3-oxetane groups, halogen atoms and/or olefinic (carbon-to-carbon doublebond) unsaturation. They can be aliphatic, aromatic or alicyclicmonomeric or polymeric compounds. The average molecular weight of thetelogen can vary from about 31 to 300,000 or even higher. However, it ispreferred that the average molecular weight be from about 31 to 4000.

Examples of telogens which can be employed are methyl alcohol, ethylalcohol, propyl alcohol, octyl alcohol, cetyl alcohol, ceryl alcohol,isopropyl alcohol, 2-methyl-2-propanol, benzyl alcohol, cyclohexanol;glycol, diethylene glycol, triethylene glycol, pinacol, polypropyleneether glycol (av. 3000), polyethylene-propylene ether glycol (av. M.W.1500), polytetramethylene ether glycol (av. M.W. 2500), polyesterglycols (adipic acid and ethylene glycol, av. M.W. 3000),propanediol-1,3, butanediols, pentanediol-1,5; trimethylol propane,tripropylene oxide adduct of glycerol, trimethylol propane monoallylether, pentaerythritol, mannitol, and the sugars such as the monoandpoly-saccharides, i.e., glucose, fructose, sucrose, rafl'inose and soforth as well as the polyfunctional polyether polyols made by reacting aminor molar amount of hexane triol or glycerine with propylene oxide orethylene oxide or other alkylene oxide and the polyfunctiona] polyesterpolyols made by reacting a minor molar amount of an aliphaticdicarboxylic acid with an excess of glycol and a small amount ofglycerine, hexanetriol, etc. and the like. Phenols which can be employedare phenol, p-monochloro phenol, p-cresol, thymol, xylenol,hydroquinone, resorcinol, resorcinol bottoms, phloroglucinol, m-, orp-hydroxy styrene, saligenin, bisphenol A, bisphenol F, 4,4-dihydroxydiphenyl, 4,4'-dihydroxy diphenyl sulfone, 4,6,4-trihydroxy diphenyldimethyl methane, long chain bisphenols having the general formula wheren and m are numbers from 1 to 4, novolac resins having a plurality of OHgroups and having the formula on OH on wUcn. O-cn.-Ucmand so forth.These diols, triols, polyols and other active OH containing materials,preferably linear or only slightly branched, can be reacted with minormolar amounts of polyisocyanates such as tolylene diisocyanate,naphthalene diisocyanate, triphenyl methane-4,4',4"-triisocyanate, etc.,to make OH containing or terminated polyurethane polyols. In place ofthe polyisocyanates, polyisothiocyanates can be used.

Aldehydes which can be used include propionaldehyde, butyraldehyde,valeraldehyde, acrolein, methyl acrolein, succinaldehyde, benzaldehyde,tolualdehyde, aldol, and so forth. Ketones which can be use are acetone,3-pentanone, 3-hexanone, 3-heptanone, methylethyl ketone,hexanedione-2,5, cyclopentanone, cyclobutanone, acetophenone, and soforth. Other useful telogens are glycidol, 1,2-epoxy butanol-4,1,2-epoxy pentanol-S, and so forth. The epoxy alcohols are considered tobe monomeric telogens since they can be incorporated in some of theinitial chain sequences to give a chain transfer site and a telomerizedgroup. Also, dihydroxy conjugated diene polymers can be used. To preparethese polymers an organic dihalide is reacted with an alkali metal toform an initiator such as M--R-M, where M is the alkali metal and R isbutane, pentane, butene, isobutene, etc., of 4 to carbon atoms. Theinitiator is then reacted with a conjugated diene of 4 to 6 carbon atomsfor example, butadiene, to form a polymer M--(BDN) (BDN) --M, x and ybeing 4 numbers such that the resulting polymer has an average molecularweight as indicated above. The polymer is next treated in solvent withoxygen to form which is treated with H 50 or HCl acid to convert the MOgroups to HO groups. If desired, these unsaturated polymers can behydrogenated to remove all or essentially all of the aliphatic doublebonds.

Still other telogens can be used such as polyvinyl alcohol, or partiallyor essentially entirely hydrolyzed polyvinyl acetate, vinylacetate-butadiene copolymers, vinyl acetate-styrene copolymers, vinylacetate-acrylonitrile or methacrylouitrile copolymers, vinylacetate-vinyl chloride copolymers, vinyl acetate-vinylidene chloridecopolymers, as well as copolymers of vinyl acetate and monomers such asdichlorostyrene, vinyl ethyl ether, ethylene, propylene, isobutylene,isoprene and the like.

Examples of mercaptans, thiols, etc. which can be used arel-pentanethiol, 2-metl1yl-l-butanethiol, 3-methyl-l-butanethiol,thiophenol, o-, m-, and p-thiocresol, 1,2-ethanedithiol, ethanethiol,furfuryl mercaptan, l-hexanethiol, thiol-naphthol, 2-propanethiol,dithioresorcinol, thioglycerol, propanetrithiol, 1,4-benzenedithiol,rnonothiohydroquinone, thiodiglycol, and thiomonoglycol and the like.The Thiokol polymers can also be used and they are generally polysulfidepolymers, which are preferably predominantly linear and liquid havingterminal 4H groups and a plurality of intralinear polysulfide linkagesconnecting recurring alkylene or oxyalkylene units; some of them may bebranched or cross-linked to some degree. Some of these materials havethe general formula:

The Thiokol polymers as well as other polythiols, thioglycols, etc. maybe reacted with minor molar amounts of organic polyisocyanates such astolylene diisocyanate, hexamethylene diisocyanate, triphenylmethane-4,4,4"- triisocyanate and the like to form SH terminatedpolythiourethanes which also can be used. In place of thepolyisocyanates, the corresponding organic polyisothiocya nates such asxylylene-u,a'-diisothiocyanate, etc. can be used for such purposes.Mixtures of the various telogens can be used.

Preferred compounds to make high functionality polyethers are thealiphatic polyols having from 2 to 6 OH groups and average molecularweights up to 4000 such as ethylene glycol, 1,5-pentane diol, diethyleneglycol, trimethylol propane, 1,2,6-hexane triol, pentaerythritol, thepropylene oxide adduct of glycerine (having a molecular weight of about260), hexose, polyalkylene ether glycols, triols, tetrols, pentols andhexols, and so forth and mixtures thereof.

The amount of monomer to be used with relation to the telogen willdepend on the ultimate purpose to be achieved. However, in general, theratio of the mols of the epoxide or monomer to the functionality(hydroxy, sulfhydryl, ketone or aldehyde oxygen) of the telogen willvary from about 350011 to 1:100. It can be said that there should be atleast 1 mol of monomer per mol telogen and at least sufficient monomershould be used to provide a plurality of new ether linkages. It will beappreciated that where a relatively high molecular weight (150,000)polyalkylene ether alcohol is desired, the mol ratio of the epoxide oroxetaue monomer such as ethylene oxide to a low molecular weight telogensuch as methanol having only one hydroxyl function will be rather high,for example, about 3400 to 1. In making a 5000 M.W. polymer frompropylene oxide and 1,2,3-tri(2-hydroxy propoxy) propane the mol ratioof epoxide to telogen is :1 and the ratio of mols epoxide to hydroxyfunctionality of the telogen is about 23:1. On the other hand, startingwith a partially or fully hydrolyzed 50:50 vinyl acetatestyrenecopolymer where it is desired to alter its crystallinity, film formingcharacteristics, reduce its heat distortion value, and the like, it mayonly be necessary to react with a portion of the hydroxyl groups to getthe desired results. In the latter case from a statistical standpoint,even if suflicient epoxides were used to theoreticall react with all ofthe OH groups, it is likely that some will not be reacted while otherswill have more than one ether linkage. It can be said that in the typeof polymerization system under consideration the epoxide or oxetane willcontinue to polymerize on the telogen as long as monomer is fed to thesystem and so long as any impurities in it do not stop polymerization ortelomerization and/or so long as the catalyst is not deactivated. Whereit is desired to modify only 5% of the OH groups of a polyvinyl alcohol(fully hydrolyzed polyvinyl acetate) having a M.W. of about 30,000 toimpart modified heat distortion properties by adding ethylene oxide, theratio of the hydroxyl functionality of the telogen to the mols ofepoxide such as ethylene oxide is :1.

This method may also be used to modify high molecular weight polymerssuch as those shown above. Thus, 'when a solution of a hydroxylcontaining high polymer, the polymerizable cyclic oxide monomer and thecatalyst are brought together the cyclic oxide would add to the hydroxylgroups. This process is usually referred to as grafting when applied tohigh molecular weight polymers but may be seen to involve the samesequence of reactions herein described as telomerization when applied tosmall molecules.

The monomers can be telomerized with the catalyst and telogen in mass(bulk), or in solvent (which can facilitate handling and transfer ofheat). They, also, can be telomerized under inert and/or non-oxidizingconditions, for example, under an atmosphere of nitrogen, argon, neon,helium, krypton or other inert atmosphere. Alternatively, the inert gascan be omitted and the monomer telomerized only under pressure from anyvaporized solvent if used, vaporized monomer or telogen. In someinstances the telomerization can be conducted in reactors containing oropen to the air provided the air is free of materials which wouldinhibit telomerization (i.e., conversion or molecular weight) andespecially free of H 0, although this procedure can be hazardous forsome of the monomers are flammable and some telomerization reactions goso fast as to be explosive. Both the monomer and telogen should besoluble in the solvent which should be an inert or non-reactive solvent.Examples of useful solvents are heptane, octane, cyclohexane, toluene,benzene, trimethylpentane, n-hexyl chloride, n-octyl chloride, carbontetrachloride, chloroform, trichloroethylene, tetrahydrofuran, dioxane(m or p), methyl tetrahydrofuran, 2- ethyl tetrahydrofuran, ethyleneglycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycoldiethyl ether, triethylene glycol dimethyl ether, diethylene glycoldimethyl ether, octaethylene glycol diethyl ether, tetrahydropyran, amylethyl ether, diphenyl ether, butyl ethyl ether, butyl phenyl ether,ethyl hexyl ether, isopropyl phenyl ether, 1,2,4,5-tetra ethyl benzene,xylene (o, m or p), 4-ethyl-o-xylene, 1-benzyl-4-ethyl benzene, phenylbutane, t-butyl benzene, 1,2-diethyl benzene, l-phenyl pentane,pentaethyl benzene, dibutyl sulfide, diethyl. sulfide, diisoamylsulfide, diisobutyl sulfide, diphenyl sulfide, di-npropyl sulfide and soforth and mixtures of the same. Preferably, since it is believed thatthe catalyst tends to be acidic when containing acidic metal halideresidues and can cause some terminal or internal unsaturation and lossof functionality, it is preferred to use basic solvents (those which cancontribute electrons or which can be considered as electron donors) suchas the organic hydrocarbon ethers (particularly the cyclic ethers andpolyethers), sulfides, and the aromatic compounds containing at leastone benzene ring disclosed herein which are non-reactive ornon-polymerizable in the present system and which have from 4 to 20carbon atoms in an amount sufiicient, usually in an amount of from about2 to 400 parts by weight,

per parts by weight of monomer(s), to reduce or prevent unsaturationand, where desired, to act as a heat transfer medium.

Since many of the reactants are volatile, the telomerization should beconducted in a closed container and may be under pressure. Pressureshould be at least suificient to maintain the liquid state fordispersion of catalyst and heat transfer although it is possible tobubble monomer into the solution. Telomerization can be conducted attemperatures of from about 0 C. to C. although somewhat widertemperature ranges can be used. Preferably temperatures of from about 15C. to 80 C. are used for telomerization. An induction period of about Ato 2 hours or more may be observed with some of the catalysts. It isvery desirable to telomerize while agitating the monomer(s), catalyst,telogen and solvent.

The catalyst generally becomes very well dispersed if not completelydissolved (molecularly dispersed) in the polymerization solution. Thus,centrifugation even after dilution in a non-viscous solvent does notusually remove a major proportion of the catalyst. Chemical methods,however, have been found useful in removing major amounts of thecatalyst. Ion exchange of the polymer in water-methanol solution hasbeen shown to reduce the conductivity of the telomer many fold byreducing the catalyst or catalyst residue content. Passage through a bedof activated alumina either with or without a prior treatment withaqueous ammonia also reduces the catalyst residue in such polymers. Thenecessity of removal of the catalyst will depend on ultimate use of thepolymer.

The propagation step of this reaction is exothermic. Some monomers maytelomerize very rapidly in the presence of this catalyst. This may becontrolled by the concentration of the catalyst, by use of a diluent,and by the proper choice of temperature. Since heat transfer duringpropagation and transfer may be critical in medium and large size batchreactors, loop type reactors can be used to reduce the induction periodby temperature cycling in the loop, for the product is a liquid orsemiliquid. Also, continuous telomerization systems may be used in whichthe telogen or monomer is fed into the system and polymer etc.withdrawn.

Gel formation during telomerization with unsaturated monomers is notusually observed using the double metal cyanide catalysts, andconsequently gel inhibitors are not normally required. Antioxidants orantidegradants such as phenyl beta naphthylamine, PBNA, or otherantidegradants are desirably added prior to or after polymerization toavoid degradation which might occur. PBNA may be used in an amount byweight approximately equal to the amount of the catalyst duringtelomerization. Some antidegradants may retard polymerization and shouldbe added after telomerization.

=In telomerizing according to the present invention, it is preferred toadd the ingredients to the reactor in the following order: catalyst,monomer and telogen. However, for many purposes all three materials canbe added at once.

Incremental addition of monomer and telogen can be used to vary themolecularweight distribution of the telomer product. When the monomer isadded incrementally, the distribution of molecular weights becomesnarrower, apparently as a result of the mass action law, i.e., when theconcentration of the monomer is lower, the transfer reaction iscomparatively favored. On the other hand; incremental addition of thetelogen leads to a wider distribution of molecular weight foressentially the same reason as above, i.e., the concentration of thetransfer agent is initially lower and thereby the propagation step isfavored.

The solvent can be added separately or mixed with one or more of theingredients. Preferably, it is added to the reactor first, or there issome solvent in the reactor prior to the addition of the otheringredients.

The polymers and copolymers (or the telomers and cotelomers) preparedaccording to the method of the present invention have average molecularweights of at least 300, preferably from about 300 to 150,000 or higher. They vary physically from light oils to tacky solids or semisolids,or even to solids. Some are one phase polymeric substances, others maycontain two phases, one an oil and the other a crystalline polymer orhigh molecular weight insoluble polymer. Depending on the telogen usedthey will have an average of from one to four or more hydroxyl groupsand a plurality of ether linkages. For example, where acetone is used asthe telogcn the resulting polymer has the general formula:

(R O) H CH1=C CHa Treatment of the telomer by mild acid hydrolysis orwith ion exchange resins removes the isopropenyl group and givesHO(RO),,H. If the telomer is a cotelomer of propylene oxide and allylglycidyl ether, acid hydrolysis or ion exchange treatment will notaffect the allyl double bonds. Monoalcohols will also givemonofunctional polymers. Diols, polyols and higher functionalitytelogens will provide telomers of the same functionality as the telogen.The polymer generally grows at one end with the monofunctional telogenand at both ends of the di (or higher) functional telogens. 'Blockcotelomers may be produced by adding various monomers alternately toincrease rigidity and so forth. The use of some unsaturated monomerspermits the resulting cotelomer to be vulcanized after extending withdiisocyanate or other extending agent into the range of useful molecularweight for Preparation of rubbers.

The telomers produced by the method of the present invention are usefulin many ways. They are useful as nonionic surface active agents, aslubricants for metal to metal surfaces, as textile sizes or finishingagents, as coolants for internal combustion engines and as hydraulicbrake fluids. They can be used to make protective coatings and films forpackaging. Telomers having average hydroxyl functionalities of 2, 3 ormore hydroxyl groups per molecule can be used in making flexible andrigid polyurethane foams (for pillows, mattresses, insulation forrefrigerators) by reaction with polyisocyanates, in the presence oftertiary amines, tin or other catalyst, silicones and so forth. Suchtelomers can also be employed in making millable (gums) or castablepolyurethanes for bushings, coatings (clothing), laminates (wall panels)etc. The liquid telomers of this invention having an average molecularweight up to about 5000 from propylene oxide or butene oxide etc. and alow molecular weight diol or triol are particularly useful in makingpolyether urethanes.

When such millable gums contain unsaturation (carbon-tocarbon doublebonds), they may be cured by conventional rubber curing proceduresdepending on the amount of unsaturation such as by using natural orbutyl rubber curing systems. The telomers of this invention, also, canbe used to make polyurethanes by reaction with phosgene and diamine.Moreover, these telomers can be reacted with mono and polycarboxylicacids to make high molecular weight polyesters. Telomers prepared fromepoxide and oxetane modified high polymers such as those of hydrolyzedvinyl acetate polymers have changes in plasticity, heat temperaturedistortion values, etc.

The polymers (telomers and cotelomers) prepared by the method of thepresent invention as well as their extension products with isocyanatesetc. may be compounded or mixed if desired with the usual rubber andplastic compounding materials such as curing agents, anti-degradants,fillers, extenders, ultraviolet light absorbers, fire resistantmaterials, dyes, pigments, plasticizers, lubricants, other rubbers,resins, plastics and the like.

8 MONOMER The organic cyclic oxides to be telomerized or polymerizedinclude any cyclic oxide (such as 1,2-epoxide, oxetane, 3-substitutedoxetane or 3,3-disubstituted oxetane) having an oxygen-carbon ring inwhich an oxygen atom is joined to 2 or 3 carbon atoms in the ring Whichwill open and telomerize with the same or other cyclic oxide monomers inthe presence of the catalyst and having up to a total of 18 carbonatoms. These monomers, also, may contain 1, 2 or more, preferably only1, aliphatic carbonto-carbon double bonds. The alkenyl, ether andhalogen (except easily ionizable halogen substituted derivatives)substituted derivatives of these cyclic oxides can likewise be employed.These cyclic oxides should be pure or essentially pure to obtain thebest results.

Examples of useful cyclic oxides are ethylene oxide (1,2-epoxy ethane),1,2-propylene oxide, 1,2-butene oxide (or 1,2-epoxy butene or 1,2-epoxybutane), 1,2-dodecane monoxide, isobutylene monoxide, styrene oxide,1,2-pentene oxide, isopentene oxide, 1,2-diisobutylene oxide, 1,2-.

hexene oxide, 1,2-heptene oxide, allyl glycidyl ether, isoheptene oxide,1,2-octene oxide, 1,2-nonene oxide, 1,2- decene oxide, 1,2-hendeceneoxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidylether, butadiene monoxide, isoprene monoxide, oxetane (C H O), tolylglycidyl ether, 3,3-dimethyl oxetane, 3-n-nonyl oxetane,3-allyl-3-methyl oxetane, 3-vinyl-3-methyl oxetane, 1,2- pentadeceneoxide, 3,3-diethyl oxetane, 3-ethyl-3-butyl oxetane, 3-chloromethyleneoxetane, 3-chloromethyl-3- methyl oxetane, 3-methyl-3-ethyl oxetane, andother cyclic oxides. Of these materials, it is preferred to use thelower molecular weight cyclic oxides such as ethylene oxide,- propyleneoxide, butylene oxide, etc. containing from 2 to 12 carbon atoms.Mixtures of 2, 3, 4, 5 or more of the cyclic oxide monomers can be usedfor telomerization.

For use in making castings and the like one or more of the above cyclicoxides can be reacted with one or more cyclic oxides having 2, 3 or morerings of from 2 t0 3 carbon atoms and 1 oxygen atom in amounts up to 20mol percent of total monomers to provide cross-linking sites in thepolymer. Examples of these cyclic oxides (i.e.,- di, tri, etc. epoxidesand/ or oxetanes) are: butadiene dioxide, limonene dioxide,bis(3-oxetane)butane, bis(3- oxetane) hexane, the reaction product ofepichlorohydrin and phloroglucinol, the reaction product of 3-chlorooxetanc and pentaerythritol, and the like and mixtures thereof.

Certain epoxide monomers have a tendency during telomerization to formtelomers exhibiting unsaturation at or near the end of the telomer inthe presence of double metal cyanide catalysts containing acidic metalhalide residues unless telomerization is conducted using a basic solventas described herein. However, in a broader sense the basic solvents willbe found useful whenever the functionalities of telomers produced withcomplex cyanide catalysts are limited by the development of unsaturatedgroups during telomerization. These epoxides are monosubstituted1,2-epoxides of the general formula having up to 18 carbon atoms andwhere R is an alkyl, alkenyl, cycloalkyl, alkoxy carbon,alkenyloxy-carbon or cycloalkyloxy-carbon group and in which breaking ofthe epoxide ring and shifting of a hydrogen atom from a carbon atomalpha to the epoxide ring to the oxygen atom can occur. The allylic orother unsaturated alcohol formed then acts as a telogen and causesformation of a monohydroxy telomer which is deleterious when the desiredproducts are diols or polyols. Examples of such compounds are 1,2-butaneoxide, 2,3-butane oxide, secondary butyl ethylene oxide, isobutylethylene oxide, normal butyl ethylene oxide, biallyl monoxide, vinylcyclohexane monoxide, propyl glycidyl ether, allyl glycidyl ether,3-tetrahydrofurfuryl ethylene oxide, 1,2-octadecane oxide, phenylglycidyl ether, crotyl glycidyl ether and the like and mmtures thereof.What is of concern here is the OH functionality derived from the telogenirrespective of the unsaturation originally present in the monomer andwhich is not affected during the telomerization by the present process.For example, a dihydroxy telomer made from 1,2- butane oxide, a minoramount of allyl glycidyl ether and ethylene glycol can be chain extendedwith 4,4'-diisocyanato diphenyl methane to make a polyurethane elastomerwhich can be mixed with compounding ingredients including sulfur, moldedand cured to form excellent solvent resistant gaskets, casters andbushings.

CATALYST The catalyst is most usefully prepared by reacting a transitionmetal cyanide complex with a metal salt in aqueous media. Removal of asubstantial amount or all of the water present in the catalyst is verydesirable to enhance the activity of the catalyst although it wouldappear that removal of all the water is not practicable and may not bedesirable. One way to remove most of the water and to enhance evenfurther the activity of the catalyst is to treat it with an additionalcomplexing or coordinating material such as an alcohol, ether, ester,sulfide, ketone, aldehyde, amide and/ or nitrile.

In general the catalysts employed in the present invention have thefollowing rational formulae:

M is a metal ion that forms a metal-oxygen bond that is relatively morestable than the coordinate bond between the metal and the nitrogen atomof the cyano, CN, group. On the other hand, M is a transition metal ionthat has more than one stable valence form and forms a relatively strongcovalent bond with the carbon atom of the CN group. An individualcatalyst can contain more than one type of M or M metal ion in itsstructure. The grouping of these metals, with the cyanide ion sharingelectrons with the two metal ions, usually exists in polymeric form asfollows: (M'CN M NC-M) where n is a number, and super 3-dimensionalpolymers can be formed depending on the coordination numbers of M and M.Moreover, of those metal ions that produce active cyanide catalysts, allcan coordinate with six groups. Most of the hexacyanoferrates (III),including zinc hexacyanoferrate (III), have a cubic face-centeredlattice as the basic structure.

The CN- group in the catalyst is the bridging group, and can constituteall of the bridging groups in the catalyst. However, other bridginggroups can be present in the catalyst so long as the catalyst containsat least a majority of CN- bridging groups. Thus, r and t are numbersand r is greater than t. t is zero when only the CN group is thebridging group. Other bridging groups, X in the righthand formula above,which can be present with the CN- group, can be F-, Cl", Br-, 1-, OH,NO, CO, H O, N0 1 C 'OE- or other acid radical, 80 2-, ONO-(cyanate),CNS(thiocyanate), NCO(isocyanate) and NCS (isothiocyanate) and so form.

In the above formulae M is preferably a metal selected from the groupconsisting of Zn(II), Fe(II), Fe (III), Co(II), Ni(II), Mo(IV), Mo(VI),Al(III), V(IV), V(V), Sr(II), W(IV), W(VI), Mn(II) and Cr(III). On theother hand, M is preferably a metal selected from the group consistingof Fe(II), Fe(III), Co(II), Co(III), Cr(H), Cr(III), Mn(II), Mn(III),V(IV), and V(V). Even more preferred catalysts of the above formulae arethose wherein M is at least one metal selected from the group consistingof Zn(II), Fe(II), Co(II) and Ni(II) and wherein M is at least one metalselected from the group consisting of Fe(II), Fe(III), Co(II), Co(III),and Cr(III). Also, a, b and c are numbers whose values are functions ofthe valences and coordination numbers of M and M, and the total netpositive charge on M times 10 a should be equal essentially to the totalnet negative charge on [M'(CN) or [M'[(CN) (X) times 0. In mostinstances b corresponds to the coordination number of M and is usually6.

Examples of catalysts which fall within the above description and whichmay be used are zinc hexacyanoferrate (III), zinc hexacyanoferratefll),nickel(II), hexacyanoferrate(II), nickel(II) hexacyanoferrateflfl), Zinchexacyanoferrateflll) hydrate, cobalt(II) hexacyanoferrate- (II),nickel(II) hexacyanoferrate(III) hydrate, ferrous hexacyanoferrate(III),cobalt(II) hexacyanocobaltate- (III), zinc hexacyanocabaltate(lI), zinchexacyanomanganate (II), zinc hexacyanochromate(III), zinc iodopentacyanoferrate III cobalt(II) chloropentacyanoferrate (H cobalt(II),bromopentacyanoferrate(II), iron(II) fluoropentacyanoferrate(III), zincchlorobromotetracyanoferrate(III), iron(III) hexacyanoferrate(III),aluminum dichlorotetracyanoferrate (III) molybdenum (IV)bromopentacyanoferrate (III) molybdenum (VI) chloropentacyanoferrate II)vanadium (IV) hexacyanochromate (H vanadium(V), hexacyanoferrate(III),strontium(II), hexacyanomanganateUII), tungsten(IV), hexacyanovanadate-(IV), aluminum chloropentacyanovanadate(V), tungsten- (VI)hexacyanoferrate(III), manganese(II) hexacyanoferrate(II), chromium(III)hexacyanoferrateflll), and so forth. Still other cyanide complexes canbe used such as In general, the complex catalysts of this invention areprepared by reacting aqueous solutions of salts which which give aprecipitate of a metal salt of a transition metal complex anion. Forexample,

where M is a metal ion which precipitates complex anion salts e.g.,Zn++, a, b and c in this equation are numbers but are not necessaryequal on both sides of the equation since their values, again, arefunctions of the valences and coordination numbers of M, M and M" andpossibly Y and Z. Z is a halide or other anion e.g., Cl-; M" is ahydrogen ion or a metal ion whose complex anion salts are soluble inwater or other solvent e.g., K+ or Ca++; M' is a complexing transitionmetal ion, e.g., Fe+++; and Y is :21 complexing anion, e.g, CN Excess MZ may be use Little if any of the other bridging groups or ligands whichcan be used to replace part of the cyano groups (CN) are usuallyintroduced into the complex by use of the salt MaZ. Rather, they areintroduced into the complex by employing the M"[M(Y) salt containing theligand or more correctly a salt having the formula M"[M[(CN),(X) inwhich I is a number dependent on the valence of M" and the other symbolsused are the same as identified above. For example, instead of potassiumferricyanide, K Fe(CN) there are used 1 1 and so forth. Examples of thepreparation of such starting materials are:

They also, may be prepared by boiling a material such as K Fe(CN) inaqueous KCl, oxalic acid or other salt and so forth. Still other methodscan be used. For example, see Cyanogen Compounds, Williams, 2nd ed.,1948, Edward Arnold and Co., London, p. 252 and elsewhere.

The salts should be reacted in substantial concentration in aqueousmedia at room temperature and, also, preferably in air or underatmospheric pressure. However, heat can be used and the catalyst can beprepared under conditions substantially or entirely free of oxygen. Thesalts which are used are the chloride, fluoride, bromide, iodide,oxynitrate, nitrate, sulfate or carboxylic acid salt, such as theacetate, formate, propionate, glycolate and the like, salt of a Melement of the group as defined above or other M salts and mixturesthereof. Preferred are the M halide salts or halide salt formingmaterials since they provide catalysts having the best activity. Anexcess of the M salt is usually reacted with a Na, K, Li, Ca etc. Mcyanide compound and so forth. Mixtures of these salts can be used.

If the resulting precipitate is then just filtered or otherwiseseparated from the Water, such as by using a centrifuge and driedwithout further washing, it has been found that the precipitated complexis non-catalytic, that is, it fails to polymerize the organic oxides inany practical amount.

Apparently, extraneous ions in the solution used to form the precipitateare easily occluded with the complex. Anions (Cletc.) coordinate to thepositively charged metallic ions in the lattice, and cations (Kcoordinate to the negatively charged nitrogen atoms of the cyanidebridging groups. These ions, especially those anions coordinating to orassociated with the M atom, inhibit catalytic activity or prevent thecomplex from causing appreciable polymerization. Additionally, theseions, for example easily ionizable Cl, may terminate the polymer chain.

On the other hand, if the complex is treated or washed one or more timeswith water, some or a substantial number of these occluded ions areremoved from the precipitate or from the surface of the crystal latticeand the complex becomes an active catalyst for the polymerization oforganic cyclic oxides. It is desired to remove all or a substantialamount of these occluded ions to enhance as much as possible thecatalytic activity of the complex. However, from a practical standpointit may not be possible to remove all of them due to the steps and timesrequired. Moreover, some of these ions are probably trapped in thecrystal lattice and cannot be removed easily. However, their presenceshould be reduced as much as possible. After the water wash the complexwill have an appreciable amount of water depending on the number ofwashings and the degree of drying following water washing. Theseresulting catalysts will then have the following rational formulae:

and/or M,,[M'(CN),(X),] (H O) where d is a number and where M, M, CN, X,a, b, c, r and t have the significance as defined supra. If the catalystis dried or gently heated for extended periods of time d can be orapproach zero.

Moreover, to obtain the best activity of the catalysts forpolymerization, an organic material or organic complexing agent is addedto the catalyst precipitate preferably before it is centrifuged orfiltered, is mixed with the water during washing of the precipitate, isused alone as the washing medium provided it replaces or dissolves theoccluded ions, or is used to treat or wash the precipitate after it hasbeen washed with water to replace at least a portion of the water.Sufficient of such organic material is used to effect these results inorder to activate and/or enhance the activity of the catalyst. Suchorganic material, also, should desirably coordinate with the M elementor ion and should desirably be one or more relatively low molecularweight organic materials. The organic material should preferably bewater miscible or soluble or substantially so, have a substantiallystraight chin or be free of bulky groups and have up to 18 carbon atoms,even more preferably only up to 10 carbon atoms, and be a liquid at roomtemperature.

Examples of organic materials for use in treating the double metalcyanide catalysts are alcohols, aldehydes and ketones such as methanol,ethanol, propanol, isopropanol, butanol, hexanol, octanol, and t-butylalcohol; formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,i-butyraldehyde, glyoxal, benzaldehyde and tolualdehyde; and acetone,methyl ethyl ketone, 3-pentanone, 2-pentanone, and 2-hexanone. Etherssuch as organic cyclic polyethers are also useful. Examples of suchcyclic ethers are m-dioxane, p-dioxane, trioxymethylene, paraldehyde andso forth. Aliphatic saturated monoethers and acyclic aliphaticpolyethers are also useful as treating agents. Examples of such ethersare ethyl ether, l-ethoxy pentane, bis-(b-chloro-ethyl) ether,bis-(b-ethoxy ethyl) ether or diglyet, butyl ether, ethyl propyl ether,bis-(bmethoxy ethyl) ether or diglyme, ethylene glycol dimethyl ether,triethylene glycol dimethyl ether, dimethoxy methane, acetal, methylpropylether, diethoxymethane, octaethylene glycol dimethyl ether and soforth of which the acyclic polyethers are preferred. Still other organiccomplexing agents can be used such as the amides, esters, nitriles andsulfides of which the following are examples: formamide, acetamide,propionamide, butyramide, and valeramide; amyl formate, ethyl formate,n-hexyl formate, n-propyl formate, methyl acetate, ethyl acetate, methylpropionate, and triethylene glycol diacetate; acetonitrile,propionitrile and butyronitrile; and dimethyl sulfide, diethyl sulfide,dibutyl sulfide, dipropyl sulfide, and diamyl sulfide and so forth.Preferred are ethers having more than one oxygen atom and which form achelate bond with respect to M. Mixtures of these organic treatingagents can be used. Excess of these organic treating agents which arenot complexed with the catalyst, especially the high boiling compounds,can be removed by extraction with pentane, hexane and so forth.

After treatment with the above organic material the catalysts have thefollowing rational formulae:

In these formulae d can be a number, fractional number, or zero and e isa number which, since the catalyst is a nonstoichiometric complex inwhich various amounts of H 0 and R may be bonded to the various Ms, maybe a fractional number rather than an integer. e is zero when thecomplex is not treated with R. R is one or more of the complexingorganic amides, alcohols, aldehydes, esters, ethers and so forth shownabove. M, M, CN, X, a, b, c, r and t have the significance as discussedabove. In general, d and e will have values correspond ing at least inpart to the coordination number of M. However, both the H 0 and R can beoccluded in the crystal lattice. In general the sum of the oxygen,nitrogen and/or sulfur or other coordinating atoms of H 0 and R(depending on the organic complexing agent) is equal to from about 0.1up to about 5.0 g.-atoms maximum per g.-atom of M. Subsequent drying orheating of the catalyst to remove all of the H 0 and/ or R results in aloss or a substantial decrease in the catalytic activity of thecatalyst.

As shown by the previous formulae if the organic complexing material isnot used, R will not be present, and hence, e can be zero. Thus, thegeneral formula for these catalysts is M3,(K)c'(HO )d'(R) where M, H O,R, a, c, a', and e have the significance as indicated above, where d ande also can be or approach zero, where K is selected from the groupconsisting of M'(CN) and and where M, CN, X, b, r and t have thesignificance as indicated above. With regard to the subscripts in theabove formulae, number includes Whole numbers as well as fractionalnumbers.

It is to be noted that if the catalyst is merely filtered or centrifugedfrom the solution in which it was prepared and washed with one of thepolymerizable cyclic oxide monomers, it shows little or no catalyticactivity for subsequent polymerization of said monomers. On the otherhand, if the catalyst is washed with water and the ether, or the etheror other organic complexing compound as described above, andsubsequently with one of the polymcrizable cyclic oxide monomers astorable initiator for polymerization is obtained.

After the washing steps, the precipitate or catalyst can be used assuch. However, it is preferred to dry it to remove excess treating agentand any remaining easily removable H and to provide it in a form whichis easily handled. Such drying is readily accomplshed my subjecting thecatalyst to a vacuum or by heating it in air or in an inert atmosphereat a temperature up to about 100 C. It is more preferred to dry under avacuum (for example 0.5-1 mm. Hg) at low temperature, for example, aboutroom temperature (25 C.) or in a stream of air, nitrogen or inert gas at25 C. or at least at a temperature above about 5 C. The heat-treatedcatalyst has generally to be used at higher concentrations than thevacuum-treated catalyst. As the temperature during drying is increased,the activity of the catalyst for polymerization is decreased. Thus, hightemperatures are to be avoided. 200 C. may be considered as a maximumtemperature. During heat treatment, it is believed that some of theoxygenated and other organic treating compounds weakly coordinated to Mmay be lost to leave voids in the crystal lattice, and the atoms in thecrystal lattice may rearrange to satisfy the coordination requirementsof the metals. Heating may also remove CN as (CN) and reduce M. Also,the molecular weight of the catalyst can increase, and the number ofexposed metal ions on the surface of the catalyst or the active sitescan be reduced, thus reducing activity of the catalyst for epoxide andoxetane polymerization. It, thus, is preferred that the drying stepleave as many as possible M ions exposed in the lattice of the complexand that the catalyst be in finely divided or particulate form to obtainthe best results for polymerization. Moreover, freshly prepared(precipitated, washed and dried) catalysts are preferred rather thancatalysts which have been aged or stored for extended periods of timesince the catalysts decompose slowly when stored. The catalyst can bestored for longer times at lower temperatures.

It is not precisely known what occurs to make the double metal cyanidecomplexes, especially those treated with the above organic complexingmaterials (ether, etc.), so useful in polymerizing organic cyclicoxides. While the following discussion relates to treatment of thedouble metal cyanide catalyst with ethers, it will be appreciated thatit will generally also apply to treatment of such catalyst with theother organic treating agents shown above It has been shown that, forexample, with respect to zinc hexacyanoferrate, as an illustration, Whenthe precipitate is washed with dioxane, a more effective catalyst isproduced. During this treatment with dioxane, it is believed that anumber of reactions take place: (1) some of the chloride ions in thelattice are oxidized, resulting in the reduction of Fe(III) to Fe(ll);(2) the chlorine from reaction l) reacts with the water and etherpresent during the wash-treatment to give Cl, and chlorinated ether; (3)the successive washes remove some of the products of reaction (2); and(4), the oxygen atoms of the ether apparently coordinate to the zincions in the lattice, rearranging the lattice structure by insertingdioxane groups between the zinc ions as follows:

Thus, in the case of some of the dioxane-zinc hexacyanoferratecomplexes, elemental analyses revealed that they were apparentlynonstoichiometric complexes having the formula Zn [Fe'(CN) (C H O (H O)where y=1 to 2 and x=2.5 to 3.1. According to infrared and elementalanalyses some of the dioxane in the complex may be chlorinated and someof the H 0 may be in the form of OH or --O-- groups. As ordinarilyprepared, these complexes generally contained from about 4 to 5% Cland asmaller amount of K+.

If the catalyst is prepared with Zn(NO' instead of ZnCl approximately50% of the normal amount of dioxane is incorporated in the catalyst.This catalyst is not as effective as the one prepared from the chloride.

Although a great part of the iron in the ether (or other organiccomplexing moiety)-zinc hexacyanoferrate complex is believed to beFe(II), as a result of the oxidationreduction reaction. that occursduring preparation, the dioxane complex prepared from ZnCl and K Fe(CN)is not as active even at polymerization temperatures of C. Analysesshowed that a reduced amount of dioxane was incorporated in suchcomplexes and the chlorine content was high.

The reduced catalytic effect when using Zn(NO or K Fe(CN) in thepreparation of the catalyst complex is apparently related to themechanism of the ether-hexacyanoferrate reaction. This mechanism may beviewed as follows. As the chloride ions of the surface zinc ions in thecrystal lattice transfer electrons into the Zn NC- Fe grouping, ethermolecules can displace the resulting chlorine atoms and form ether-zinccoordinate bonds. For example,

(Note: y in the above equation may not be same as in the precedingformulae.)

The driving force for this reaction is the removal of C1 by solution ofthe gas in the water and ether and the reaction of C1 with the ether.

This oxidation-reduction reaction and displacement of the chlorine byether is accomplished by a change in the crystal lattice. According toelemental and infrared analyses, most of the zinc ions in the latticeappear to form coordination bonds with from 1 to 4 oxygen atoms. Theoxygen atoms of both the water and the ether are involved in thiscoordination. X-ray analysis and density measurements appeared to confirm this lattice change. Thus, the oxygen atoms of the ether competewith the CN groups of the Fe(CN) anion to produce a polymeric structurewith more exposed zinc ions as shown below:

This process of opening up the lattice is aided by the presence of waterduring the ether treatment. Apparently, the water dissolves Fe(CN) anionsections in the lattice that are coordinated to K+ ions, and more of thelattice becomes exposed to the ether during the hexacyano-ferrate-etherreaction.

One technique for removing water from the lattice structure is todisplace the Water with ether and remove the former by azeotropicdistillation. The distillation is best carried out under vacuum at roomtemperature or thereabouts, i.e., 5 to 40 C., in order to preventdecomposition of the complex which may occur at elevated temperatures asdiscussed supra. In any event temperatures should not go above 100 or200 C. as discussed supra or below about, 5 C. Hexane or otherrelatively lowboiling, inert, and essentially water-insoluble solventssuch as heptane, toluene, benzene, pentane, 2-chlorobutane, cyclohexane,cyclopentane, ethylene chloride, and butane can be used in thisdistillation to separate the water from the ether as the distillatecollects in a trap. In this way, all displaceable water is removed,however, some water usually invariably remains trapped in the lattice.Other methods can be used to remove the water.

Chloride ions can inhibit the polymerization reaction. Several methodsfor reducing the ionizable chlorine or other ionizable anions in thecatalysts can be used. For example, in one method the catalyst is washedwith a solution containing ether and water and the soluble chloride saltis removed. In another method the zinc hexacyanoferrate is prepared byreacting compounds such as AlFe(CN) or Li Fe(CN) with ZnCl Thecorresponding halide that forms and occludes on the crystals of Zn[Fe(CN) is then removed by the ether during the washing operation. Whenthe preparations are made with K Fe(CN) ether-insoluble KCI is produced.However, when zinc hexacyanoferrate is prepared by the second methodabove, ether (organic treating agent) soluble CaCI AlCl or LiCl isproduced. Also, where ions such as C1 are covalently bound to thecomplex, they do not apparently adversely affect polymerization of theepoxides and oxetanes. In fact, the organic complexing materials likethe chlorinated ethers can improve the efiiciency of the catalyst,because the halogenated ethers can be displaced more readily by thecpoxides and oxetanes to start polymerization than the nonhalogenatedethers.

When the catalyst is treated with polyethylene glycol ethers, a veryactive catalyst is obtained. They apparently form a chelate bond to thezinc ion. The formation of a chelate complex increases the driving forceof the hexacyanoferrate-ether reaction and makes for a very open latticebecause polymeric coordination through the oxygen atom is prevented. Thecoodination of with diglyme (dimethyl ether of diethylene glycol) isshown below:

The use of diglyme and diglyet (dimethyl and diethyl ethers,respectively, of diethylene glycol) in the usual catalyst preparationwas found to increase the efficiency of the catalyst.

Moreover, the addition of a substantial amount, such as -70% by volumeof the total fluid, of the ether (or other organic treating agent) tofreshly precipitated hexacyanoferrate in water greatly enhanced theactivity of the catalyst. According to elemental analysis, this complexmay have some (ZnCl) ion in its structure.

It, thus, would appear that the best catalyst for oxide polymerizationare those that contain the greatest amount of Zn-O ether bonds, ratherthan Zn-OH O bonds, and the least amount of ionizable chlorine. The moreactive catalysts, also, are prepared by using an excess of zinc chlorideand adding the K Fe(CN) solution to the chloride.

The catalyst is used in a minor amount by weight only sufficient tocatalyze the reaction. Large amounts are usually wasteful and may intime cause reversion or subsequent decomposition of the polymer ortelomer. In some cases, use of large amounts of telogen to reduce themolecular weight may require extra amounts of catalysts. Also, forexample, one telogen may require the use of more catalyst than anothertelogen. In general, there is used a total of from about 0.001 to 15% byweight of the catalyst based on the total weight of the polymerizable ortelomerizable cyclic oxide monomer or monomers employed duringtelomerization. However, it is preferred to use from about 0.01 to 1.00%by weight of the catalyst based on the total weight of the monomer(s).

In the case of many inorganic preparations where precipitates are to beformed, it is usual to employ an excess of one of the reactants to drivethe reaction forward or to obtain the desired yield. Consequently, theprecipitate which forms can contain some of one or more of the reactantsor a co-precipitate. In the preparation of the double metal cyanidecatalysts it is generally desirable to employ an excess of an M metalsalt, i.e., ZnCl which is co-precipitated with the desired double metalcyanide. Washing with water removes some of the salts like the excessZnCl Repeated washings will remove more of the ZnCl until the catalysthas a very low chloride or ZnCl content. Such a catalyst is useful inthe preparation of telomers wherein the unsaturation is virtually nilalthough more catalyst must be used. Moreover, the repeated washings anddryings of the catalyst are time consuming and the resulting telomer hasa broader molecular weight distribution. It is preferred to wash withwater and the organic complexing agent for a limited number of times orto a limited degree to obtain the highest catalytic activity. A telomeror polymer with a broad molecular weight distribution may be desirablefor some purposes but they are generally of higher viscosity anddifficult to mix. It is preferred in making polyurethane foams to have anarrower molecular weight distribution for the polyol in order to bettercontrol the foaming action and final properties of the foam and toprovide polymers wih much reduced amounts of unsaturation. On the otherhand, the catalyst need not be washed so extensively with water and thecomplexing agent but rather in an amount sufiicient to remove asubstantial amount of the zinc salt yet provide a measurable amount ofthe zinc salt in the catalyst which also contains the complexing agent.Such a catalyst possibly due to the presence of the salt may beconsidered as acidic and with certain monomers as defined above (RHC CHZwill provide telomers having undesirable unsaturation. On the otherhand, if a basic solvent is used during the telomerization, such acidiccatalysts will provide the desired telomers with little or nounsaturation and with a narrower molecular weight distribution employingconsiderably less catalyst. Such catalysts will have the general formulaM,,(K) -(I-I O) -(R),,-(M(J) where M, a, K, c, d, R and e are the sameas discussed above. m is a number equal to the valence of M and n is anumber (fractional or whole). I is a halide of a metal salt which givesa precipitate of a metal salt of a transition metal complex halide, forexample, chloride, and bromide. Further information on the preparationof double metal cy- 17 anide catalysts is disclosed in US. Pat. Nos.3,278,457; 3,278,458; 3,278,459 and 3,404,109.

Mixtures of these catalysts can be used.

EXAMPLES 18 a mortar and pestle and then placed in a nitrogen flushedbottle. The catalyst was Zn [Fe(CN) -H O-dioxane. Vacuum treatment of aportion of the catalyst at about 100 C. would show that it containedabout 13% by weight of liquid analyzing 20-30% Water and 8070% Thefollowing examples will serve to illustrate the di present inventionwith more particularity to those skilled P tion of catalyst for RunsSA-B and 4A above. in the art 55.04 gms. of calcium cobalticyanide wasdissolved in Example 400 ml. of water. This was added dropwise to 44.98grams The catalyst, Zn3[Fe(CN)6]2.H20.dioxane in one case of zincchloride (10% excess) dissolved in 200 m1. of andZn3[Co(CN)6]2.H20.acetone in another, was added water. The catalyst wasthen centrifuged and the decant to a citrate bottle flushedwith Nfollowed by propylene S F The catalyst was then washed wlth acetoneoxide and then acetone as the telogen, flushed with N Fi f f decaldlscarfki The Procedure8 of and capped. The capped bottle was thenrotated in a h g centl'lfugmg and decantmg were ep three constanttemperature water bath for a predetermined more tlmes- The catalyst wasthen P 111 a i d of i Th amounts f materials d, i f oven at roomtemperature to dry. The dried material was telomerization, bath ortelomerization temperature and pulverized y means of a mortal and p TheZinc results obtained are shown in Table A, below: cobalticyanide, Zn[Co(CN) -H O-acetone, obtained TABLE A Telomerization conditionsCatalyst Results Concen- Appeartration, Acetone, Converance HydroxylUnsatuwt. Temp. Time, sion, at about content, ration, Viscosity, percent2 percent; d. percent C. 3 mm./g cps.

0.10 2 s0 1s 84 HO 0.31 0.10 10 so is 80 L0 0.70 0.20 2 80 13 100 MO0.35 0.20 10 s0 is 100 L0 0.84

A 0.20 2 00 18 100 HO 0.58 .013 3 B.. 0.20 10 00 is 100 M0 1.14 .0221,121 0.03 2 so 24 71 MO 0.30 0.14 2,803 B 0. 0a 10 so 24 76 L0 0.830.20 287 4A Z113[C0(CN)6]2 0.01 0 70 24 17 1 Catalyst also contained H2Oplus dioxane or acetone as indicated above.

2 Based on the weight of the propylene oxide. 3 L=light; M=mediu1n;H=heavy; 0 =oil. gilt-e5 treatment with ion exchange resin.

Preparation of catalyst for Runs lA-D and 2AB,'

above.

was a white powder. A portion of a catalyst prepared in the same way wasplaced in a Pyrex tube at 100 C. Dry nitrogen gas (lamp grade) was blownthrough the tube and into a U-tube in a Dry Ice bath. About 12.8% byweight of liquid was collected of which about :5% was acetone and about25% i5 was water as determined by gas chromatography.

Example 2 Propylene oxide was polymerized with Zn ['Fe(CN) 'H O'-dioxanecatalyst using various telogens according to the method of Example 1,above. The polymerization conditions and results obtained are shown inTable B, below:

TABLE B Telomerization conditions Results Appearance Zm[F8(CN)a]2Temper- Converoi polymer Run concentration Wt.perature, Time, slon peratabout No. Wt. percent; Telogemtype cent; '0. hrs. cent 25 C.

A--- 0.20 Hexanedione-2,5 4 20 40 H0. 21 0.20 d 20 80 10 MO.

' A..- 0.10 Propionaldehyde-- 2 s0 10' 04 Mo. 22 0.16 do 1- 10 S0 10 16L0. A.-- 0.10 Methy1ethy1ketone 2 00 10 no. 23 B-.. 0.16 do 10 80 16 98HO. A--. 0.10 Cyclopentanone 2 00 10 33 LG. 24 0.16 do.... 10 60 16 51MO. A.-- 0.16 Methanol. 0.2 00 10 100 no. B-.. 0.16 0.... 2.0 60 16 100H0. 25 0.16 do 10.0 60 24 60 L0.

'4.-- 0.10 tert-Butanol 0.2 00 10 100 Tacky solid.

0.16 do 2.0 60 16 100 HG. C--- 0.16 do 10.0 60 24 77 HO.

1 Based on the weight of the monomer.

I Monomer to Polyme 19 The catalyst for Runs 20A-B to 25A-C, above, wasprepared by the following procedure. 49.5 gms. of

K Fe(CN) were dissolved in 300 ml. of water. 76 gms. of AgNO 20 solvedin 60 m1. of H was added to the Ca [Fe(CN) solution. After sufiicientagitation, the solution and precipitate were centrifuged. The solutionwas discarded and the precipitate was washed with dioxane. After washingwith dioxane, the precipitate was centrifuged and the dissolved in 100ml. of water were added to the dioxane discarded. The washing,centrifuging and decant- K FB(CN) ing (discharge of dioxane) wasrepeated three times. The 3 6 catalyst was then dried under a vacuum atroom tem- SOllltlOIl- After sufiiclfint Stlmng the a )6 was perature.The density of the catalyst was 0.2507 g./cc. filtered from thesolution. The Ag Fe(CN) calculated 10 E am 16 3 to weigh 80 grams waswashed with 800 ml. of water and X P filtered again. After two washingswith 800 m1. of Water, The method of this example was similar to themethods the Ag Fe(CN) was added to 500 ml. of water. 27 gms. of thepreceding examples except that the catalyst used of CaCl dissolved in100 ml. of water was added to the was the same type of catalyst as usedin Example 1, Runs Ag Fe(CN) slurry. After sufiicient agitation, theAgCl 3A-B and 4A, above, other telogens were used, and in was filteredout of the solution and discarded. The solusome cases, other monomerswere employed. The amounts tion calculated to contain 40.5 gms. of Ca[Fe(CN) of monomers used, telomerization conditions and results wasplaced in a 1000 ml. beaker. 33.4 gms. of ZnCl disobtained are shown inTable C, below:

TABLE 0 Telomerization conditions Monomer(s) Telogen Cata- Mole Molelyst, Mole per- Comonper- Wt. perper- Temp Time, Run number Monomer centl omer cent 1 cent Type cent hours 0.16 5.0 so 24 0.08 2.5 80 24 0. 043.2 so 24 0.04 0.6 80 24 0.12 a s0 24 0.12 1 s0 24 0.04 9 s0 24 0. 04 3s0 24 0. 04 1 s0 24 Results Unsatu- Yield, Kinematic 0H ration, Acid Runnumber percent viscosity number mm./g. No. Remarks A 75 66.6 0.031 *0.14 Foams prepared from mixtures con- 1, 261 32.7 0.051 0.04 taining andof the material together with LG-56. Dry and stable although weaker thancontrol. 0. 68 10-12 0.01 0.1 M.W. (0smotic)-37-57X10 Heavy oil Thickpaste Medium oil Heavy oil Very Heavy oil Based on total 100 mol percentof monomer (s) 2 Allyl glycidyl ether. 5 1,2-epoxy butane.

Inherent viscosity in benzene.

' Propylene oxide.

LG-56, N lax Triol LG-56," is a propylene oxide adduct of glycerolcontaining substantially -95% secondary OH radicals, an OH number ofabout 56. and an average molecular weight of from about 2,8003,l00.Experience has shown that appreciable amounts of monofunctional materialin polyurethane foam formulations leads to chain breaking and collapsewhile significant amounts of non-functional material gives thepolyurethane foam a sticky feel. The foams were prepared by the oneshotprocess.

11 Sticky paste. 1! Tacky solid.

Example 4 TABLE F.-POLYPROPYLENE ETHER GLYCOLS Unsatura- Monoiunctrontionality,

Molecular wt. from percent of mol hydroxyl number end groups percent 1Commerically available polypropylene ether glycols.

2 Calculated from suppliers products bulletin. 3 Polypropylene etherglycols prepared as described above by present mven ion.

TABLE D Telogen Catalyst Molecular wt. conc., wt. C0nc., wt. Temp.,Yield,

percent 1 Type percent 1 C percent 1 Cale. Found Viscosity Run number:

. 033 67 60 37 15, 000 t 9, 500 1. 37 067 2. 7 60 55 5, 300 4 4,670 i 8239 10. 7 60 72 2, 160 4 2, 400 6 .17 .53 'IMPG) 10. 7 50 90 1, 260 I 1,310 1 579 13 5. 4 50 100 5, 100 i 3, 900 1 2, 790 26 10. 7 50 100 2,7006 2,330 1 887 1 Based on weight of monomer charged.

1 (JP-260, tri(propylene oxide) adduct of glycerol, Dow Chemical 00.,molecular weight about 260, generally 1,2,3-tri (Z-hydroxy-propoxy)propane.

3 Trimethylol propane. 4 End group analysis assuming triol formation.Mecrolab Osmometer. Intrinsic in benzene. 7 Kinematic cs. at C ICrosslinked when reacted with diisocyanate; 86.5% insoluble in benzene.This shows that the polyol obtained had a functionality greater thantwo.

Example 5 The method of this example was similar to that of the 30Molecular from preceding examples. One of the catalysts used was 8.

TABLE G Polypropylene ether triols Unsaturation percent hydroxyl number:of end groups Zn [Co(CN) compound prepared using acetone ac- 3030: 3cording to the method of Example 1, above. Another 3000 1 4 Zn [Co(CN)catalyst was prepared according to the 4040 9 method of Example 1,above, except that glyme, ethylene 4000 1 3 glycol dimethyl ether, wasused in place of acetone. The 5000 1 12 monomer was propylene oxide,various multifunctional 3900 2 telogens were used, and thepolymerization conditions 3900 2 and results obtained are shown in TableE, below: 1 Commercially available p yp py e et er t o s.

a Propylene ether triols prepared as described above by presentinvention. TABLE E Wt. percent Telogen Product mole wt. Zn; Go(CN)o]1catalyst Viscosity catalyst based, on C0nc., Pzn. By end Vapor ofproduct Run prepared wt.ot g./100 g. of temp, group pressure, cs. atnumber wi monomer Type monomer 0. analysis osmometer 25 C.

' .0625 1.0 so .0875 Ethylene glycol... 1.5 125 3. 0 50 .033 1.3 60 .066Pentanedio1-l,5 2.7 60 l3 5. 3 60 .13 Resorcinol 5.9 50 d .07 BisphenolA12.1 50 54A Acetone .5 Polytetra- 100.0 25

hydrofuranl 55A Glyme .07 RJ-IOO 2 33.0 50

1 Molecular weight of about 1000.

2 Partially hydrolyzed styrene-vinyl acetate copolymer, hydroxylfunctionality of 5.4, brittle solid at 25 0., and molecular weight ofabout 1500.

3 Viscous liquid.

Example 6 Polypropylene ether glycol telomers of several differentmolecular weights were prepared by the method of this invention asgenerally shown with respect to the preceding examples from pentanediol-1,5 as the telogen and propylene oxide as the monomer. Trioltelomers, likewise, were prepared according to the present method usingCP-260 (tripropylene oxide adduct of glycerol, see above) as the telogenand propylene oxide as the monomer. These diols and triols of thepresent invention as used in this example were stripped to removeresidual monomer but not treated to remove the catalyst nor end groups.Those polymers were then compared with polyurethane grade commerciallyavailable polypropylene either glycols and triols (prepared from KOH) asto their percent unsaturation. The monofunctionality of the diols wasalso compared. The results obtained are shown in Tables F and G, below:

The determination of monofunctionality was made considering that only OHand olefinic end groups should exist and that the unsaturation wouldappear where otherwise an OH group would be present. The sum of theequivalents/mole of hydroxyl and of olefinic unsaturation is thus takento be 2 for diols. The data in Table F show that the hydroxylfunctionality of the various diols at about the 1000 molecular weightlevel is about the same but that at the higher molecular weight levelsthe hydroxyl functionality of the diols prepared by the method of thepresent invention is much closer to the theoretical functionality. TableG, above, shows similar results with respect to the triols. Again,triols prepared by the telomerization process of the present inventionhave a much higher hydroxyl functionality (low unsaturation) thanthecommercial triols.

Example 7 Telomer polyether diols and triols were prepared by themethods similar to those of the preceding examples using the Zn [Co(CN)catalyst treated with glyme. The monomer was propylene oxide and thetelogen was pentane diol-1,5 for making diols and CP-260 (see above) formaking triols. These telomers were only stripped to remove monomer, seeExample 6, above. The diol telomers were then reacted or chain extendedwith 2,4-tolylene diisocyanate at 120 C. for 40 hours using 0.035 partby weight of stannous octoate to speed the reaction to form linearpolyurethanes. Similar extensions were made with the telomer triols. Themaximum hardness was determined for the diols, and the minimum amount ofswelling for the triols. Similar experiments were run on commerciallyavailable polyurethane grade polypropylene ether glycols and triols madeusing KOH and the results obtained are shown in Tables H and I, below:

TABLE H Maximum hardness of resulting polyurethane 1 Molecular weight ofpolypropylene ether glycol:

1 Williams plasticity. b Polypropylene ether glycol telomer made asdescribed a ove.

A series of extensions with TDI was done on each sample of polyetherglycol. With excess polyether glycol or excess of TDI lower hardnesseswere observed. Hence, the polyuretrligme represent about a 1 :1 molratio of polyether glycol to I. 4 Commercially available polypropyleneether glycol as described above.

TABLE I Index of minimum swelling of resulting polyurethane, 70 hours at75 F. in toluene Molecular weight of polypropylene ether triol:

1 Polypropylene ether triol telomer made as described above. 2Commercially available polypropylene ether triol as described above.

The above results show that with respect to the telomer diols producedby the present invention much higher molecular weight linearpolyurethanes can be obtained. In the case of the telomer triols of thisinvention stronger polyurethanes were obtained. In this case the extentof swelling of the resulting polyurethanse was measured. Thismeasurement gives an indication of the strength of the network obtained,i.e., the lower the value, the greater the strength which is related tothe functionality of the triol at a given molecular weight. With greaternetwork formation or greater strength the toluene has much moredifliculty in penetrating and swelling the polymer.

Example 8 The reaction of phosgene with an organic compound havinghydroxyl groups results in the formation of a chloroformate. Thechloroformate group can react with an amino group to form a urethanelinkage. Accordingly, a

dichloroformate can react with a diamine to form a poly- TABLE I DiamincPolyurethane obtained Polypropylene for chain ether glycol extending LowM.W. Intrinsic viscosity molecular chloroiormate polymer weight of PPEGadded Solvent Value 3,305 1 Pi CHzCl-z 0.85 3,470 d CHZC12 0. 35 2,000m-Oresol--.- 2. 35 2,000 1 HMDA do 99 b Polypropylene ether glycoltelomer of present invention as described a ove.

2 Commercially available material as described above. 3 Dichloroformateof 1,4-butane diol.

The above results show that polyurethanes made with the telomers of thepresent invention give much higher viscosities and consequently highermolecular weights than polyurethanes made with commercially availablepolypropylene ether glycols.

Example 9 Polyurethane foams were prepared using liquid triol telomersof this invention as well as commercially available triols by theone-shot process in which the polyol was fed to a mixing head from asupply container, the tolylene diisocyanate was fed from anothercontainer to the head, and the activator mixture was fed fromv anothercontainer to the mixing head where all of the ingredients were mixedtogether rapidly and quickly discharged to a mold and the mixtureallowed to foam. The activator mixture generally comprises the blowingagent, dispersing agent and catalysts although one or more of thesematerials may be in the polyol or polyisocyanate stream so long as theydo not prereact with the polyol or polyisocyanate. The materials used inmaking the polyurethane foams and the results obtained are shown inTables K and L below:

TABLE K.FORMULATIONS FOR POLYURETHANE FOAMS Run number 60 61 62 63 64Materials, parts by weight- Triol 1 100 3 100 2 100 4 100 4 100 CCl F3.0 3.0 8. 0 3. 0 3. 0 Silicone 1. 5 1. 5 1. 5 1. 5 1. 5 Stannousoctoate-" 0. 27 0. 27 0. 27 0. 2O 0. 10 Lead. naphthenate 0. 10 0. 10 0.l0 0. 10 0.05 /20 mix of 2, 4/2, 6-

tolylene dlisocyauates 49. 0 49. 0 40. 0 49. 0 49. 0 Water 4. 0 4. 0 4.0 4. 0 4. 0 N -methyl morpholine 0. 60 60 0. 60 0. 60 0. 60 Tetramethylbutane diamine 0. 05 0. 05 0. 05 0. 05 0. 15

1 Polypropylene ether triol having a molecular weight of about 3,000.Propylene oxide adduct of glycerine. Commercial material.

1 Same as 1 but containing about 0.024% by weight of the Zn;[Co- (CNlilicatalyst treated with glyme as disclosed in preceding examples.

3 'Iriol telomer of this invention prepared as in preceding examplesfrom propylene oxide and CP-260 (see above) and having a molecularweight of about 3,000 and containing 6% of a diol telomer of thisinvention prepared as in the preceding examples from propylene oxide andpentane diol-1, 5 having a molecular weight of about 2,000 to increasestrength.

4 Triol telomer of this invention prepared as in preceding examples frompropylene oxide and (JP-260 (see above) and having a molecular Weight ofabout 3,000.

6 Dow Silicone 201. A polysiloxane-polyoxyalkylene block type copolymer.

TABLE L.-PHYSICAL PRfiQgAlfiilIES F POLYURETHANE Run number so 51 e2 636 Density, p.01 1 31 1. 28 1. 32 1. 33 1. 44

12. 7 14. 8 12. 6 11. 3 1. 6 1. 9 1. 3 1. 1 110 160 140 110 Schopper(cracked) 42 45 44 42 Link loads in lbs., 12" x 12 x 2":

25% 24. 0 26. 0 2A. 0 27. 5 27. 0 65 45. 0 50.0 46. 0 51. 0 53.0 25%return 18.0 19. 5 17.0 20. 0 20. 0 Percent recovery. 75. 0 73 71 74 74Load ctor 1. 87 1. 92 1. 92 1. 89 1. 96 Compression set (80%) 15. 5 8. 28. 7 6. 8 4. Du Pont static fatigue test, lo

25%. 27. 1 34. 0 29. 2 27. 3 29. 6 65 15. 6 38. 0 21. 7 19. 6 28. 3AS'IM be in load at The above data show that the polyol telomersproduced by the method of the present invention are useful in makingpolyurethane foams having properties comparable to those from foams madewith commercially available 26 The resulting polymers were liquids.These results show that liquid polyethers also can be obtained usingmercaptans as telogens.

Example 11 Several telomerizations were carried out in which the monomerwas 1,2-epoxy butane in the presence of tetrahydrofuran as the solvent.The solvent, telogen and part of the monomer were added with thecatalyst, a zinc cobalticyanideglyme complex having the general formulaZn [Co(CN) prepared with glyme as shown above pared by reacting anaqueous solution of zinc chloride with an aqueous solution of calciumcobalticyanide. After slowly mixing the two solutions, glyme was added,the mixture centrifuged and the clear solution discarded. The catalystprecipitate was then twice reslurried in glyme and centrifuged, or twicereslurried in a mixture of water and glyme and centrifuged followed byanother reslurry in glyme and centrifugation, followed by vacuum dryingat 50 C. The telomerization was conducted in a sealed reactor undernitrogen, and after the initial reaction, the balance of the monomer wasadded incrementally over a period of several hours. The times andtemperatures employed, reaction conditions and results obtained areshown in Table N, below:

TABLE N Millimoles of THF, unsaturation Catalyst, wt. Telogen, per gramof wt. percent wt. telomer percent of of monpercent of Time, (polyol)Run number monomer omer Telogen monomer Temp;, 0. hours obtained Notes04 0 Hexylene glycol-.- 4. 3 50 (80) 42 (3)# 0. 14 Oil.- .04 0 d0 4.1 5030 0.18 Oil. 06 4. 1 30 0. 17 Oil. 04 4. 1 50 (80) 57 (1) 066 Oil. 04 4.1 50 (80) 57 (2) 039 Oil. 08 4. 3 50 42 0 020 0H# 31.3,

liquid. 16 4. 3 50 42 0. 022 DE? 32.5,

liquid. 14 6. 1 50 24 0. 013 OH# 47.0,

liquid. 04 4. 1 80 (50) 6 (6) 0. 014 Oil. 08 4. 1 50 48 0. 015 Oil. .083.6 50 48 0.016 Oil. 12 3. 0 80 (50) 4. 5 (24) 032 OH# 41.6

NOTE.#=5D C. for 42 hours, then 80 C. for 3 hours. Similar conditionsfor Runs D, E, I and L.

polyols. Run 62 shows that the cyanide catalyst does not visibly affectthe properties of the commercial polyols. The polyol telomers of Runs61, 63 and 64 were stripped after preparation to remove residual monomerbut were not otherwise treated.

Example 10 Table N shows the results of telomerizations of 1,2- buteneoxide with an without tetrahydrofuran (THF) as a solvent. It will benoted that in the absence of THF the products had unsaturation contentsof from 0.14 to 0.18 millimole per gram. When made in the presence of 60percent THF, the products had unsaturation contents of from 0.014 to0.022 millimoles per gram. It will also be noted that at six and twentypercent THF concentration unsaturation content values fall intermediatebetween the extremes. Thus it seems rather clear that the unsaturationof poly-1,2-butylene ether glycols is reduced according to the amount ofbasic solvent in which it is made.

Example 12 The method of this example was similar to that of Example 11,supra, except that 1,2-epoxybutane was telomerized in the presence ofvarious solvents. The

1 Nonamethylene dimercaptan; t Thiophenol.

telomerization conditions and results obtained are shown below in TableTAB LE 0 Catalyst, Solvent, Telogen, Telomer wt. perwt. perwt.perunsatcent of cent of cent of uration, Run Number monomer Solventmonomer Telogen monomer Temp, C. Time,hours mm./g.

. Hexylene glyc0l 4.1 50 (80)# 57 (2)# 039 20 1,4 butanedioL. 3. 6 50(80) 23 (4) 023 20 do 3.6 80 30 .044 2 do 3. 6 50 (80) 30 (4) 046 .16 do8 .do. 3.6 50 (80) 30 (4) .026 16 Methyl THF..-. 20 .do- 3. 6 50 (80) 23(4) 048 l6 Dioxane 20 do. 3. 6 50 (80) 23 (4) 071 12 Benzene 20 do 3. 680 35 080 08 Hexane 20 do 3. 6 80 30 167 N orE.#=See Table N, supra.

All above products were liquids.

alcohol which in turn can act as a telogen for a portion of Table 0shows the effect of certain other solvents in 20 the 1,2-butene oxide:comparison to the effect of THF. The effect of temperature on theunsaturation content of this polymer is also H 4- shown. Gly-me, i.e.,1,2-dimethoxyethane, methyl- CHCH=CH CHOH and tetrahydrofuran, dioxaneand benzene appear to have a 0 25 Com lex definite effect of loweringthe unsaturation whereas hexane CH3 CH=CHCHIOH cHacHzcfilcHz 1 has muchless of an effect if any. Cyanide It is not precisely known what occursduring telomeriza- Catalyst tion using acidic catalysts and basicsolvents but it is becH.oH=oH-cH,o- Gin-0H0 H lieved that sinceincreasing the temperature has the effect of increasing theunsaturation, one effect of the so'lvent would be to allow moreefiicient heat transfer from the Catalyst Particles, monomer 1 m f thusThe monohydroxyl telomer so produced when mixed with would lower thePemperatufe at whleh the feeetlolls a the telomer from the intentionallyadded telogen thus can Place e 1f thls were the {01211 effect, It doesnot reduce the average functionality of the product obtained. seemplausible to expect large differences between the Exam 1 13 effect ofsolvents with approximately the same molecular p e weights (and thus thesame molecular mobility). Par- The method of this example was similar tothat of Exticularly compelling is the difference between the effectsamples 11 and 12, supra, except that propylene oxide was of 20 percentTHF and hexane which gave products hav- 40 the monomer used. Thetelomerization conditions and reing unsaturation contents of 0.04 and0.17 respectively. sults obtained are shown below in Table P:

TABLE P Catalyst, Solvent, Telogen, Telomer wt. per wt. perwt.perunsaturacent of cent of cent of Temp., Time, tion, Run number monomerSolvent monomer Telogen monomer O. ours mm./g. Notes 0 Hexylene glycol4.3 .005 0 lA-butanediol 1.8 .007 OH# 246 6 Hexylene glycol- 4.3 .004 0do 4.3 .003 4.3 .007 5.8 .001 OH# 7318 1.8 .005 0H# 24.1 .4.6 .0134 OH#56.3 4.6 .0146 OH# 57.9 .04 2.0 .006 OH# 28.4 2.9 .0025 OH# 27.3 4.5.0016 OH# 66.6 3.0 .0036 3.6 .0032 .04 Dioxane 4.3 .007 .04 Benzene 4.3.005 .04 Hexane 4.3 .004

No'rE.-#=See Table N, supra. All above products were liquids.

Table P shows the effect of solvents on the unsaturation ofpolypropylene ether polyols made with complex cyanide catalysts. Herethe effect is not nearly as clear as with poly-1,2-butylcne etherpolyols. The unsaturation of the telomers is already quite low andfurther reduction is difficult to measure. Also other factors mayaccount for the formation of some of the nnsaturation found in some ofthe products. However the results at 80" C. are fairly convincing that asuppression of the unsaturation has been obtained in THF. Also it seemssignificant that there was one run in THF with an unsaturation contentsmall proportion of 1,2-butene oxide isomerizes to crotyl of 0.001millimoles per gram although others, with and 29 without THF, hadunsaturation contents of from 0.003 to 0.007.

It is of interest to note that an cpoxide, itself an ether, may in somecases perform this function during its own polymerization. Indeed thismay be the reason telomers of propylene oxide have such low unsaturationvalues. On the other hand, as the molecular weight of the monomerincreases within a homologous series, this effect may be lessenedthrough polarity or dilution. This was found to be the case whencomparing the unsaturation of poly-1,2- butylene ether glycols made inTHF and methyl-THF.

What is claimed is:

1. The method of making polyethers having at least one terminal hydroxylgroup and an average molecular weight of between about 300 and 150,000which comprises:

(1) polymerizing in the liquid state at a temperature of from about to180 C. at least one polymerizable organic cyclic oxide monomer selectedfrom the group consisting of ethylene oxide; 1,2-propylene oxide;1,2-butene oxide; 1,2-dodecane monoxide; isobutylene monoxide; styreneoxide; l,2-pentene oxide; isopentene oxide; 1,2-diisobutylene oxide;1,2-hexene oxide; 1,2-heptene oxide; allyl glycidyl ether; isohepteneoxide; 1,2-octene oxide; 1,2-nonene oxide; 1,2-

1 decene oxide; 1,2-hendecene oxide; methyl glycidyl ether; ethylglycidyl ether; phenyl glycidyl ether; butadiene monoxide; isoprenemonoxide; oxetane, tolyl glycidyl ether; 3,3-dimethyl oxetane; 3-n-nony1oxetane; 3-allyl-3-methyl oxetane; 3-vinyl-3-methyl oxetane;1,2-pentadecene oxide; 3,3-diethyl oxetane; 3- ethyl-3-butyl oxetane;3-chloromethylene oxetene; 3- chloromethyl-3-methyl oxetane and3-methyl-3-ethyl oxetane with (2) at least one telogen having amolecular weight up to 4000 selected from the group consisting of methylalcohol; ethyl alcohol; propyl alcohol; octyl alcohol; cetyl alcohol;ceryl alcohol; isopropyl alcohol; 2- methyl-2-propanol; benzyl alcohol;cyclohexanol; glycol; diethylene glycol; triethylene glycol; pinacol;polypropylene ether glycol; polyethylene-propylene ether glycol;polytetramethylene ether glycol; propanediol-1,3; butanediols;pentanediol-1,5; trimethylo1 propane; tripropylene oxide adduct ofglycerol; trimethylol propane monoallyl ether; pentaerythritol;polyether polyols made by reacting a minor molar amount of hexane triolor glycerine with propylene oxide or ethylene oxide; 1,2,6-hexane trioland the propylene oxide adduct of glycerine, in admixture with (3) adouble metal cyanide complex catalyst in an amount of from 0.001 to 15%by weight of said monomer, said catalyst having the general formula:M,,(K) -(H O) -(R) where K is selected from the group consisting of:

where M is at least one metal selected from the group consisting ofZn(II), Fe(II), Fe(III), Co(11), Ni(II), Mo(lV), Mo(VI), Al(III), V( V),V(V), U W( V), W(V 0 and Cr(III),

where M' is at least one metal selected from the group consisting ofFe(II), Fe(III), Co(II),

30 Co(III), Cr(II), Cr(III), Mn(II), MnflII), W(IV), and V(V), where Xis at least one material selected from the group consisting of F, Cl,Br, I'", OH'", NO=, CO, H20, NO2 C2O4=, 804 CNS", NCO", and NCS', whereR is an organic material containing 1 to 18 carbon atoms substantiallywater miscible selected from the group consisting of alcohols,aldehydes, ketones, esters, ethers, amides, nitriles and sulfides, wherea, b and c are numbers whose values are functions of the valences andcoordination numbers of M and M with the total net positive charge on Mtimes a being essentially equal to the total negative charge on (K)times 0, where r and t are numbers, r being greater than t, where d iszero, or a number, and where e is zero or a number sufficient toincrease the activity of M,,(K) -H O for the polymerization of saidmonomer. the ratio of the mols of said monomer to the number of hydroxylgroups of said telogen being between about 3500:1 to 1:100.

2. The method of claim 1 wherein said temperature is between 15 and C.

3. The method of claim 1 wherein said polymerization is conducted in thepresence of a solvent for said monomer selected from the groupconsisting of tetrahydrofuran; 1,2-dimethoxyethane; methyltetrahydrofuran; dioxane; benzene and hexane.

4. The method of claim 1 wherein said catalyst is a zinchexacyanocabaltate complex with a polyalkylene glycol.

5. The method of claim 1 wherein said telogen is propylene glycol.

6. The method of claim 1 wherein said cyclic oxide is ethylene oxide orpropylene oxide. 2

References Cited UNITED STATES PATENTS 2,141,443 12/1938 Stanley et a1260615 B 2,448,664 9/1948 Fife et al. 260-615 B 2,723,284 11/1955 DeGroote 260-615 B 2,807,651 9/1957 Britton et al. 260-615 B X 2,942,0336/1960 Leis et al. 260615 B X 2,965,658 12/1960 Kirkpatrick 260-615 B X2,996,550 8/1961 Simons 260-615 B 3,117,998 1/ 1964 Cosby et al. 260-615 B 3,278,458 10/1966 Belner 260-2 3,336,242 8/1967 Hampson et al.260-615 B X 3,404,109 10/1968' Milgron 260-615 B X FOREIGN PATENTS6611403 2/1967 Netherlands 260615 B HOWARD T. MARS, Primary ExaminerU.S. Cl. X.R.

25251, 52 A, 426, 428, 430, 431; 260-26 P, 27.5 NC, 77.5 AP, 209 R, 429X, 484 R, 484 B, 484 P, 495 R, J, N, 607 A, 609 F, 613 B, 615 B $223?"UNITED STATES PATENT OFFICE 1 CERTIFICATE OF CORRECTION r 'F I v 5 pm;August 13 197M In reucor(s) "Rcbe'rt Johnston Hercld I v v har tif iedthat: error appears in the above-identified patent and that, said.LettersPatent' are hereby cdrrected as shown below:

I 9 juline' 29 which reads; "M IM' (QN)' X) T I should read I I M w[(CN) (X) l Qlumn '95 line #1, which reads; I 'n" h d i' Cl T...M4..1 Ic1y1'..) .v

'Column: line 30;, which reads: "Zn ]Fe CN) NO i 1 should read ---Zn [FNO 1 10, line #2, which reads: "necessary" should I readj- -necessarilyvI 12, line 11, which reads: "chin" should read f- ----Ch&l, il'1------ Lv v Column 13, line 28, which reads: "accomplshed my" 7 should read-accomplished by---..

fife- 111mmiu, 1ine 65, which reads: "00 1-1 0 should read 9: U I-'-'-OC H Column 16, line 50, which reads: "wih" should read----wich-'--..

' "Table B,, un'der heading which reads: "Temperature, "C."

' should read -.---Temperature,C. f

" Table C, under Mole percent 5 (Run number 330 reads: ["3- should, read---1, 2 I

Vii-$050 (5/ Patent No. 3, 9,5 5 Dated August 13, 197A Invent1f(s)Robert Johnston Herold It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 21, line 72, which reads: "either" should read ---ether---.

Column 23, line 61, which reads: "polyurethanse" should read---polyurethanes---.

Table M, heading which reads: Telogen conc., et.

percent on wt. of monomer" should read -'--Telogen conch, wt. percent onwt. of monomer----.

Table M, heading which reads: "Hydroxy number" should read ---Hydroxylnumber---.

Column 26, line L7, which reads: an should read ---and---'.

Table P, under heading Run number, which reads: "3:"

should read --l3---.

Table P, under heading Notes (Run F which reads "0H#7318" should read---OH#73.

Column 29, line 39, insert ---hexylene glycol--- before "pinacol".

Column 29, line H3, delete "tripropylene oxide adduct of glycerol".

Column 29, line H7, change the "5" to ---and---.

Column 29, lines L7- L8, delete "and the propylene oxide adduct ofglycerine J k i I I Pa "UNI ED STATES PATENT OFFICE V v 569 CERTIFICATEOF CORRECTION mm No. 3, 9,5 5 mud August 13, 1971:.

Inventor) Robert Johnston Herold It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected asvshown below:

Column 30, line L, which reads: "NO should read Column 30, line 5,before'CO" add ---o Column 30, lines 22-25 delete "the ratio of the molsof said monomer to the number of hydroxyl groups of said telogen beingbetween about 3500:1 to l:l0O.".

Column 30, line 26, which reads: "between 15 to 80C."

should read ---from about 15 to 80C.---,

Column 30, cancel claims Nos. 4 and 5.

Signed and sealed this 29th day of October 1974.

(SEAL) Attest:

,McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents

